Novel n-(3,5-dihalophenyl)-imide compounds

ABSTRACT

Novel N-(3,5-dihalophenyl)imide compounds, which exhibit a strong antimicrobial activity against microorganisms including phytopathogenic fungi, parasites of industrial products and pathogenic microorganisms, represented by the formula,   wherein X and X&#39;&#39; each represent halogens and A represents a substituted ethylene such as chloroethylene, C1-C4 alkylthioethylene, C1-C2 alkyl-ethylene or 1,2-di-C1-C2-alkylethylene, a cyclopropylene such as 1,3-dimethylcyclopropylene, trimethylene, a cyclohexylene-1,2-, cyclohexenylene-1,2-, cyclohexadienylene-1,2- or o-phenylene. The N-(3,5-dihalophenyl)imide compounds can be obtained by any of methods which produce imide compounds or reaction of an N(3,5-dihalophenyl)maleimide compound with a mercaptan, a hydrogen halide, phosphorus chloride or thionylchloride.

United States Patent [191 Fujinami et al.

[4 1 Sept. 2, 1975 [73] Assignee: Sumitomo Chemical Company, Ltd.,

Osaka, Japan [22] Filed: Jan. 9, 1973 [21] Appl. No.: 322,169

Related US. Application Data [62] Division of Ser. No. 17,339, March 6,1970, Pat. No.

[30] Foreign Application Priority Data Mar. 19, 1969 Japan 44-21529 July2, 1969 Japan..... 44-25795 Apr. 11, 1969 .lapan..... 44-28585 Apr. 19,1969 .lapan..... 44-30455 May 9, 1969 Japan.... 44-35919 May 27, 1969.Iapan.... 44-41504 May 28, 1969 Japan 44-41874 [52] US. Cl. 260/281[51] Int. Cl C07d 39/00 [58] Field of Search 260/281 [56] ReferencesCited UNITED STATES PATENTS 3,098,002 7/1963 Riddell ct al. 260/2813,125,583 3/1964 Leonard 260/281 3,159,637 12/1964 Falbe.... 260/2813,166,571 1/1965 Izzo 260/281 3,660,408 5/1972 Ackermann 260/281 OTHERPUBLICATIONS Jour. Org. Chem. Vol. 26, p. 4126 (1961).

Corey et al. .lour. Am. Chem. Soc. Vol. 89 pp. 3912-3914 (1967).

Von Auwers et al. Chem. Abstracts Vol. 28 C01. 5413 (1934).

Fujinami et al., Chem. Abstr. Vol. 75 C01. 5516f (1971) abstracting So.Africa 7,001,624 (October 1970) Primary Examiner-Donald G. DausAttorney, Agent, or FirmStevens, Davis, Miller & Mosher [57] ABSTRACTNovel N-(3,5-dihalophenyl)imide compounds, which exhibit a strongantimicrobial activity against microorganisms including phytopathogenicfungi, parasites of industrial products and pathogenic microorganisms,represented by the formula,

wherein X and X each represent halogens and A represents a substitutedethylene such as chloroethylene, C,C alkylthioethylene, C,Calkyl-ethylene or l,2-di-C,C -alkyl-ethylene, a cyclopropylene such as1,3-dimethylcyclopropylene, trimethylene, a cyclohexylene-1,2-,cyclohexenylene-l ,2-, cyclohexadienylene-1,2- or o-phenylene.

The N-(3,5-dihalophenyl)imide compounds can be obtained by any ofmethods which produce imide compounds or reaction of anN-(3,5-diha1ophenyl)maleimide compound with a mercaptan, a hydrogenhalide, phosphorus chloride or thionylchloride.

4 Claims, No Drawings NOVEL N-( 3,5-DIHALOPHENYL)-IMIDE COMPOUNDS Thisis a division of application Ser. No. 17,339, filed Mar. 6, 1970, nowUS. Pat. No. 3,745,170.

The present invention relates to novel N-(3,5- dihalophenyl)imidecompounds and their production and use.

The said N-(3,5-dihalophenyl)imide compounds are represented by theformula,

wherein X and X represent halogen atoms, and A represents a substitutedethylene group of the formula,

(l' H-R -CHR- wherein R is alkyl of l-4 carbon atoms, halogen, alkylthioof l-lO carbon atoms, lower alkenylthio, lower aeylthio, aralkylthio,phenylthio, halogenated phenylthio, methylated phenylthio, nitratedphenylthio, di-

alkylamino (the alkyl group has l-6 carbon atoms), cyclic secondaryamino of 4-5 carbon atoms, morpholino, alkylsulfinyl of 1-10 carbonatoms or aralkylsulfinyl, and R is hydrogen, alkyl of l-4 carbon atomsor halogen, provided that R is alkyl if R is alkyl, R is halogen if R ishalogen, and R is other than alkyl if R is hydrogen, or A represents acyclopropylene group represented by the formula,

wherein R R R and R each represents hydrogen or alkyl of l-4 carbonatoms, or A represents trimethylene, cyclohexylenel ,2-,cyclohexenylene-l ,2-, cyclohexadienylene-l ,2- or o-phenylene.

In the present invention, examples of the halogen atom include chlorine,bromine, iodine and fluorine, and examples of the cyclic secondary aminogroup include pyrrolidino and piperidino.

It has now been found that the said N-(3,5- dihalophenyl)imide compoundsof the formula (1) exhibit a strong anti-microbial activity against awide variety of microorganisms including phytopathogenic fungi andparasites of industrial products, and some of them further possessstrong anti-microbial activity against pathogenic microorganisms. Thisfinding is unexpectable and surprising because compounds analogousthereto such as the corresponding 3,5-unhalogenated derivative show noappreciable anti-microbial activity. 1n this connection, it may be notedthat some of such analogous compounds exert a strong herbicidalactivity, whereas the compounds of the present invention have noherbicidal action.

A fundamental object of the present invention is to provide the novelN-(3,5-dihalophenyl)imide compounds (1) having a marked anti-microbialactivity.

Another object of the invention is to provide a pro- 5 cess forpreparing the N( 3,5-dihalophenyl )imide compounds (1).

Other objects will become apparent from the following description.

In accordance with the present invention, the N-( 3,5-dihalophenyl)imide compounds (I) are prepared according to any of theprocedures represented by the equations shown below.

PROCEDURE 1 In the case where, in the aforesaid formula (1), A is otherthan an alkylsulfinyl ethylene or aralkylsulfinyl ethylene group, i.e. Ris other than an alkylsulfinyl or aralkylsulfinyl group:

In the case where, in the formula (I). A is a substituted ethylenegroup, in which R is hydrogen and R is alkylthio, lower alkenylthio,lower aeylthio, aralkylthio, halogenated phenylthio, methylatedphenylthio, nitrated phenylthio, dialkylamino, cyclic sec- 45 ondaryamino, morpholino or halogen:

PROCEDURE 3 1n the case where, in the formula (I), A is a substitutedethylene group, in which R is hydrogen and R is chlorine:

ll Dmpc-tmiipfir-on P0,, or soc], o

PROCEDURE 4 1n the case where, in the formula (1), A is a substitutedethylene group, in which R is hydrogen and R is alkylsulfinyl oraralkylsulfinyl:

In the above-mentioned formulas of the procedures 1-4, X and X are asdefined previously, A is a substituted ethylene group represented by theformula,

wherein R is as defined previously, and R is alkyl of 1-4 carbon atoms,halogen, alkylthio of 1-1() carbon atoms, lower alkenylthio, loweracylthio, aralkylthio, phenylthio, halogenated phenylthio, methylatedphenylthio, nitrated phenylthio, dialkylamino (the alkyl group has 1-6carbon atoms), cyclic secondary amino of 4-5 carbon atoms or morpholino,provided that R, is alkyl if R is alkyl, R, is halogen if R is halogenand R, is other than alkyl if R is hydrogen, or a cyclopropylene grouprepresented by the formula,

wherein R;,, R R and R are as defined previously, or trimcthylene,cyclohexylene-l,2- cyclohexenylenel,2-, cyclohexadienylene-l,2-, oro-phcnylenc; R is alkylthio of 1-10 carbon atoms, lower alkenylthio,lower acylthio, aralkylthio, phenylthio, halogenated phenylthio,dialkylamino (the alkyl group has 1-6 carbon atoms), cyclic secondaryamino of 4-5 carbon atoms, morpholino or halogen; R is alkyl of 1-10carbon atoms, aralkyl or lower alkenyl.

On the basis of each of the above-mentioned procedures, the process ofthe present invention is explained below.

PROCEDURE 1 This procedure is due to the dehydration reaction of amonoN-(3,5-dihalophenyl)amide of dicarboxylic acid compound (II).According to this procedure, all the N-( 3,5-dihalophenyl )imidecompounds of the present invention can be synthesized, except the casewhere A in the formula (I) is alkylsulfinyl ethylene or aralkylsulfinylethylene. When this procedure is adopted, the desiredN-(3,5-dihalophenyl)-imide compounds (la) can be easily prepared bymerely heating the mono-N- (3,5-dihalophenyl)amide of dicarboxylic acidcompound (II) to 150-250C., preferably 180-200C., or by bringing thesaid compound (11) into contact with a suitable dehydrating agent at20-l50C., preferably -10()C. Examples of the dehydrating agent includeacid anhydrides such as acetic anhydride, phosphorus pentachloride,phosphorus oxychloride, phosphorus pentoxide, acetyl chloride andthionyl chloride, but particularly preferable dehydrating agent isacetic anhydride. The amount of the dehydrating agent is more than anequimolar amount of the compound (II). The dehydration reaction proceedseven in the absence of a reaction medium, but is preferably effected inthe presence of a heating medium or a solvent. Examples of the heatingmedium include xylene, liquid paraffin. nitrobenzene, dichlorobenzene,etc., and examples of the solvent include benzene, toluene, xylene,chloroform, carbon tetrachloride, etc. The reaction terminates in aperiod of 30 minutes to 10 hours, in general.

In the case where, in the formula (ll), X is identical with X and thegroup A is not symmetric, there are two kinds of plane structure isomersas the starting mono-N-(3,5-dihalophenyl)amide of dicarboxylic acidcompound (11). No matter which starting material is used, however, theresulting N-( 3 ,5- dihalophenyl)imide compound (la) is same instructure.

The mono-N-(3,5-dihalophenyl)amide of dicarboxylic acid compounds (11),which are used as the starting materials in this procedure, are novelcompounds and are easily obtainable by reacting, for example, acorresponding 3,5-dihaloaniline with a corresponding acid anhydride, asshown in the following equation:

o X ll NH,+O A x ll (VII) (VIII) PROCEDURE 2 This procedure is due tothe addition reaction of N-(3,S-dihalophenyl)maleimide compounds (III)to carbon-carbon double bonds. The said addition reaction isaccomplished by merely bringing the N-(3,5- dihalophenyl)-maleimidecompound (III) into contact with an equimolar amount or slight excess ofa compound represented by the formula (IV). The reaction temperaturevaries depending on the kind of R but, in general, is to 100C,preferably 0 to 30C., in case R is alkylthio, lower alkenylthio, loweracylthio, aralkylthio, phenylthio, halogenated phenylthio, methylatedphenylthio, nitrated phenylthio, dialkylamino, cyclic secondary amino of4-5 carbon atoms or morpholino, and is 0 to 100C, preferably to 50C., incase R is halogen. The above-mentioned reaction is preferably effectedin a solvent. The kind of the solvent used varies depending on the kindof Rf. Generally, however, the solvent is selected from benzene,toluene, xylene, aliphatic hydrocarbon, solvents weak in polarity suchas ether, chloroform, etc., dioxane, tetrahydrofuran, dimethylformamide,dimethylsulfoxide and the like. Further, in case R is other thanhalogen, a suitable basic catalyst is used. Whereby the reactionprogresses easily. Examples of the basic catalyst include tertiaryamines such as triethylamine, dimethylaniline, diethylaniline, pyridine,N-methylmorpholine and the like. Particularly, the use of triethylamineis preferable.

The N-(3,5-dihalophenyl)maleimide compounds (III), which are used as thestarting materials in this procedure, are easily obtained by reacting,for example, a corresponding 3,5-dihaloaniline with maleic anhydride(refer to Dutch Patent Application No. 68-17250 filed by SumitomoChemical Co) which corresponds to US. Pat. No. 3,586,697.

PROCEDURE 3 This I procedure is due to the reaction of N-(3,5-dihalophenyl)maleamic acid compounds (V) with a chlorin ating agent. Thesaid reaction is effected by bringing the N-(3,5-dihalophenyl)maleamicacid compound into contact with an equimolar amount or slight excess ofphosphorus pentachloride or thionyl chloride at 0 to 80C., preferably 20to 80C. If necessary, the reaction is carried out in a suitable solvent.Examples of the solvent include chloroform, carbon tetrachloride,chlorobenzene, etc.

After completion of the reaction, the reaction product is washed withwater, dried and then recrystallized from a suitable solvent such as,for example, benzeneethano], petroleum benzin-benzene, ligroin-benzeneor n-hexane-benzene, whereby the desired product can be easily obtained.i

- The N-(3,5-dihalophenyl)maleamic acid compounds (V), which are used asthe starting materials in this procedure, are readily obtainable byreacting, for example, a corresponding 3,5-dihaloaniline with maleicanhydride.

PROCEDURE 4 This procedure is due to the oxidation reaction of thioethercompounds (VI). The oxidation reaction is easily accomplished bybringing the thioether compound (VI) into contact with at least astoichiometric amount of a suitable oxidizing agent such as, forexample, hydrogen peroxide, an organic peracid, i.e. performic,peracetic or perbenzoic acid, chromic acid or permanganate, at 0 to40C., preferably 20 to 30C. In the case of employment of chromic acid orpermanganate, it is desirable that the oxidizing agent is not used inlarge excess. The reaction is desirably effected in a solvent. Examplesof the solvent include water and watermiscible solvents such as acetone,alcohol, acetic acid and the like. The thioether compounds (VI), whichare used as the starting materials in this procedure, are obtainedaccording to the aforesaid procedure 1 or 2.

The N-(3,5-dihalophenyl)imide compounds (I) obtained in the above mannerare purified, if necessary, by a suitable means, eg by recrystallizationfrom a proper solvent.

As mentioned previously, the N-(3,'5-dihalophenyl)- imide compounds (I)of the present invention exert a strong anti-microbial activity againstvarious microorganisms including phytopathogenic fungi (e.g. Pyricu-[aria oryzae, Coclzliobolus miyaheanus, Xant/zonmnus oryzae,Sphaerot/zeca fillginea, Pellicularia susakii, Pellicularia filamentosa,Fusarium 0.\' \-sporum, Corticiunz rolfsii, Bolrytis cinereu,Sclerorinia sclerotiorum, Aller- Izariu kikuc/zimzu, Alternaria mall,Glomemlla cingulutu and Pyt/zium aphanidermatum) and parasites ofindustrial products (eg Aspergillus niger) and pathogenic microorganisms(e.g. Staphylococcus aureus, Escherichia coli, Tric/10p/1 \"l0n rubrum).

Further, the characteristic physiological activity of the presentcompounds is observed only in the case where 3,5-dihalophenyl groupshave been substituted in the nitrogen atoms of the imide compounds, andis not observed at all in the case where other phenyl groups have beensubstituted therein. In order to substantiate this and the fact that thepresent compounds have such strong and broad microbicidal effects as notseen in microbicides of the prior art, typical test results are setforth below.

TEST 1 Each of the test compounds in the form of wettable powders wasdiluted with water to a given concentration and sprayed to rice plants,which had been cultured in pots of 9 cm. in diameter and grown up to the3 leaves stage, in a proportion of 7 ml. of the dilution per pot. Afterone day, the plants were inoculated by spraying with a spore suspensionof Ppfcularia oryzae. 5 Days thereafter, the number of diseased spotswas counted. The results were as shown in the tables below, from whichit is understood that the N-(3,5- dihalophenyl)imide compounds (I) arestronger in antifungal activity (against Rice blast) than compoundsanalogous thereto such as the corresponding other isomeric compounds.

Table 1 N0. of Concent- Diseased No. Compound ration spots (pvp.m.) perlo leaves II c-c11.sc11. c111 ,c11 l D-N 1 1.000 28 C] c c11 Cl i; z

CCHS-Q-Cl 3 I 1,000 8 c CCH 0 cl ll 1-\ CCHN 0 4 N 1,000 36 cl CCH,

CCHS 5 N I 1.000 12 Br C- CH2 Reference compound 0 I c cn s 6 N I 1.000256 CCH:

Untreated 286 Table 2 Table 2-Continued No. of No, of Concent- DiseasedConcent- Diseased No. Compound ration spots No. Compound ration spots(p.p1mv) per 10 (p.p.m.) per lo leaves leaves Reference compound c c1 111 :I N 1000 31: c

C 4 Q: N l-000 264 11 C 0 ll Cl ll c1 C 2 @i N 56 C 60 Referencecompound ll Cl 0 0 II C II Reference compound 5 N Q 281 0 C 11 3 C 0 CUntreated Z Table 3 Table 4-Continued No. of Conccm- Diseased C C tD1101 No. Compound ration spots per On-en beflse v I 5 No. Compoundrat1on spots per p p m ea (p.p.m.) leaf 0 CH\ H cl Untreated 34.5

CH C 1 1 N 500 is -C C] (3H:x ll

0 Table 5 O CH \I C Br CH Concent- Diseased 2 l N 500 No. Compoundration spots per CH\C/ Br (p.p.m.) leaf cH,, II o 1| c c1-1.socn. ,c1-1

1 N 500 1.4 CH3 \C CH I Cl 1 CH O 3 1 N 500 36.7

C H, Untreated 38,8 cnz, I1

Untreated 389 TEST 2 Each of the test compounds in the form of dusts wasTable 4 applied to rice plants, which had been cultured in pots No of of9 cm. in diameter and grown up to the 4 leaves stage, Concent- Diseasedin a proportion of 100 mg. of the dust per pot by use Compound P2 F of aduster. After one day, the plants were inoculated .m. (121 Pp by spraymgw1th a spore suspens1on of Coclzlmbolus C1 0 m1' \-abeuru1s. 3 Daysthereafter, the number of diseased CH spots was counted. The resultswere as shown in the ta- 1 1 500 bles below, from which it is understoodthat the N-( 3,5- C g- Ii cl d1halophenyl)1m1de compounds (I) arestronger 1n anti- 0 fungal activity (against Helminthosporium leaf spotof rice) than compounds analogous thereto such as the i cl correspondingother isomeric compounds CH C\ 2 I /N 500 1.4

C H-,-C

' II G 2mm No. of Com: nt- Cl B No. Compound raugn 322:8911

I CH-C (PP- h) m 3 /N 500 1.2 o C H ,-C C1 ll ,c CllS'Cli -Cl-l O l N l3 500 3 c cu Reference compound 01 H 2 Cl 0 CH c 4 1 \N-Q 500 33.8 01 f,c CH-S-CH2(GH on 11 2 11 l 2 2 3 00 o O c ca 1 1| 2 Reference compound0 Cl 0 CH (i i ll c1 5 1-1-- i 1 1o 500 3013 c ca s (H -C 5 r\' l 500 Oc 011 \l 01 11 O 0 Reference compound c1 I, ,5 cl

CH C\ 4 N/C (Ill S Cl 500 6 6 I /N@ 500 35.1 c CH2 CH.,C C1 ll ll 3 0 m0Cunlinucd No. of No. of Concont- Concnntd M No. Compound ration 32:?Compound 2mm; 222:

' (p.p.m.) D 1 0 p.p.m. O I ll c1 0 N Br 7 c m/ c c ca n c1 f Br 0 CH 0CH I 3 w N 2 9.2 3

0/ 3 N 2.0 1.8 H Br (4 CH\ c 0 C11 u 1 ll 01 c O 4 N 2 3.5 C II c Q c 01ll 01 cu o 4 L n 2.0 0.3

H c f 01 o 2 5 O \l (:1 c

H 2 5 4 5 Reference compound I! 01 o o I cs cu c Roferonco compound 5 lN 2.0 68.4

o CH\ 0 0 ll ll H3 0 s Q: 11 2 78.1

fi Reference compound 0 o C H3 c1 und CH Blhrcnco compo 6 I N 2.0 56.2

fi ca c ll 7 Q: C\ 2 59 s CH3 0 I c1 Reference compound Cl Referencecompound g\ 0 '1 l N C1 2.0 0.1 CH C/ a @i N Q 2 73.2 cn g H C11 0Untreated 67.3

Reference compound Table l l 0 a No. of 9 OE p 2 70,4 ConccntdiseasedNo. Compound ration spots ll (/1 pcr leaf 0 Cl Untreated 76-9 C l l' NQ.0 o

Ho. 02 B Goncentr Io. compound ration :3 2 c I 2 .0 0. x

(5) h CH -C\ N ll 3\ (:1

0H" 14 C 1 LE /11 2.0 0 l] sk 01 O Table l l-Continued Table ll-Continued No. of No. of Concentdiseased Cone-em diseased N0. Compoundration spots No Compou nd ration spots (71) per leaf per leaf Cl CIReference compound CH 3 I N 2 0 2.4 CI T CH -c c 1; CI Cl 0 x I I N NO 20 53.2

CH C ll Cl O C] O Br 4 N o 0 L1 Reference compound CH C|i Cl Br 0 CH c 9I N 2 o 70.7 Br 0 CH -C c| ll (H-C O 5 N 2 L9 CH-C cl Reference compoundBr 0 C] O l Reference compound CH C 10 l N 0 2.0 58.1 Cl 0 C 2 ll ll CHCO 6 I I N Cl 7 O 60.9

CH C Reference com ound ll p Cl 0 Cl 0 ll Reference compound CH C l l IN 2 O 63.2 c1 0 cl ll CH CH'C ll 3 7 l N 2 0 54.6 0

CH-C ll Cl Untreated Cl 0 Table 12 No. of Coneentdiseased No. Compoundration spots per leaf 0 Cl ll CCH-SOCH CH l N l 2.0 0

CCH. cl

0 Cl ll CCH-SOCH. ,(Cl'-l. ),;CH: 2 N I 2.0 3.5

CCH. Cl 0 0 Cl ll CCHSOCH. ,(CH. ,CH, I 3 N I 2.0 1.8

- 0 Cl I! C-CHSOCH 4 N l 2.0 0.3

CCH.. Cl

Untreated 66.7

TEST 3 Each of the test compounds in the form of emulsifiableconcentrates was diluted with water and applied to rice plants, whichhad been cultured in pots of 9 cm. in

wherein the infection index was determined on the basis of the followingcriteria:

Infection index Infectious state 5 0 No infectious spots on the sheaths.diameter and grown up to 5060 cm. in height, in a pro- 1 Infectiousspogfike Shades portion Of 10 ml. of dllUtlOn per pot. After 3 hOUI'S, a2 Infectious spots of less than 3 cm. mycelium-disc-inoculum ofPeIIicu/aria sasakii was ap- 3 Infectious spots of not less than pliedonto the sheaths. 5 Days thereafter, the infectious 3 Cm in Sim state ofthe sheaths was observed, and the degree of damage was calculatedaccording to the following 10 equation: The results were as shown in thetables below, from Inf f N b which it is understood that the N-(3,5-Degree EG Z; 2;; dihalophenyl )imide compounds (I) are stronger in antigTotal number X100 fungal activity against Sheath blight of rice thancomama C g of stems 15 pounds analogous thereto.

Table 13 Concent- Degree No. Compound ration of (p.p.m.) damage 0 cl llCCHSCH- .CH 1 N 200 2.7

C -c1-i Cl 0 CCHSCH2(CH- ,)2CH;, 2 N 200 0 CCH CI 0 0 cl H CCHS- 3 N l-200 o C-CH2 Cl 0 0 Cl II c cH scl 4 N 200 1.8

C-CH Cl 0 0 Cl I C-CHSCH2 s N 1 l 200 3.9

C-CH-- Cl 0 0 cl ll C-CH-N Q 6 N I 200 18.9

CCH, .CI n 0 0 Br ll CCHS 0 7 N 1 200 0 CCH ll Reference compound 0 llCCH-S Q s N l 200 86.9

CCH.

9 TUZ 200 3.6

Untreated l ()0 methylarsine bi$( dimethyldithincarbamatc) and 2071 (byweight) of zinc dimethyldithiocarhamate.

Table 14 Table l6-Continued Coneent- Degree Concent- Degree No, Compoundration of No. Compound ration of (p,p.m.) damage g (p1p,m.) damage H 01CHC 1211/ 11 Br c c CH, ll Cl 2 11 c I! C/N-Q 200 5.2

11 c1 3 I N 200 2.8 0 15 CH-C 2 II 1:11 o 0 01 R, \C C\ Referencecompound 3 c 11 200 o 0 11 611- c CH ll '4 c1 CHC 4 l N 200 100 CHC 1:110 CH ll ll Br 0 H/ CL c/ Reference compound 11 Br 0 c1 0 ll CH-C R 5 NCl 200 100 aference compound 0 CH II II 0 CH C\ C N 5 R E 100 Referencecompound II 6 TUZ 200 413 o Untreated 100 Untroltnd 100 Table 15 40Table l 7 Concent- Degree No. Compound ration of damage Concenb Degree 0No. Compound ration of CH g Cl (p.p.m.) damage 1 CH., L N 1000 14.5 0

- CHWC Cl II c1 C| CH C CH -C a Reference compound ll 0 0 ll C H C O 2CH N 10000 100 Br 1| C| -r- CH C II 2 N Q 500 3.6 O C H- .C a

Untreated 100 0 c1 ll c1 CHC 3 I N 500 4.5 Table 16 01 ll Concent-Degree 0 No. Compound ration of (p.p.m.) damage Reference compound 6 O O5 C I ll c1-1 l1 c1 CHC CHC 4 N c1 500 1 l N 200 0.8

Table l7-Continued Concent- Degree No. Compound ration of (p.p.m.)damage Reference compound Cl ll CH-C N 500 I00 CH-C C Cl Rcfercncccompound 0 Cl ll CH C 6 N 800 I00 C H. .C ll 0 Reference compound 0 Clll CH c 7 N 500 I00 CH C Reference compound 8 TUZ 500 3.7 Untreated 100Table 18 Concent- Degree No. Compound ration of (p.p.m.) dama- 0 cl ll CCHSOCH. ;CH l N\ I 500 O C-CH, Cl

O I II C C CH-SOCH. (CH CH 2 500 3.6

c CCH.

O Cl CCHSOCH. 0 3 N 500 0.4 c C-CH;

Reference compound 4 TUZ 500 3.8 Untreated l ()0 TEST 4 Farm soil wascharged into ots of 9 cm. in diameter, and a soil 10 ml.) infected withPelliculuria filamentosa was dispersed over the surface of said soil.Each of the test compounds in the form of emulsifiable concentrates wasdiluted with water to a given concentration, and the dilution wasapplied into each pot in a proportion of ml. per pot. After 2 hours, 10seeds of cucumber were sowed therein. 5 Days thereafter, the infectiousstate of the grown seedlings was observed, and the percentage of standwas calculated according to the following equation:

Number of healthy seedlings Percentage lll treated plot X of standNumber of germinated seedlings in untreated and uninoculated plot Theresults were as shown in the tables below. from which it is understoodthat the N-(3.5-dihalophcnyl)- imide compounds (I) are stronger in soildisinfectant activity than compounds analogous thereto.

Table 19 Concent- Percent- No. Compound ration age of (p.p.m.) stand 0II CCHS.CH .CH l 500 98.0

c CCH,

0 CI ll CCHS- 2 N\ 500 I00 Cl i 0 cl ll C-CH-S-Q- CI 3 N 500 97.0

c cH. cl u 0 cl ll CCHSCH 4 DN I 500 83.4

c-cn, Cl

0 cn cn. cl ll CCHN 5 \cHzcHz 500 78.8

C-CH Cl CCH-S 0 N 500 91.0

CCH Br I] Untreated 0 (Inoculated) Untreated (Uninoculatcd) 100 Table 20Percent- No. Compound age of stand ll Br CHC 1 H C 1.000 93.8

cH c Br O CH, O

ll Cl CH, C 2 c I N- 0 1,000 1000 H CH C ll Cl 23 24 Table ZO-ContinuedTable 22 Concent- Pereent- Concent- Pereenb N0. Compound ration age ofN0. Compound ration age of (p.p.m.) stand (p.p.m.) stand C H;, O

I ll 1 f c N l 000 90 1 I c U H CH C N 500 87.8

I l() o ll Cl Reference compound n 3 C1 CH C C 4 CH N G L000 0 7 @E C500 87.

I! Cl 0 0 Reference compound 0 ll cl C c| cl 3 ED: N 500 90.2

C I 5 cl No 1,000 9307 II O C Ci Reference compound U I t d O n tea 0 CUntreated 4 g: 500 0 (Uninoculated) 100.0 u *Fungicide used as soildisinfectant. 0

Reference compound CI CI Table 2] cl N0 500 864 c Cl Conccnt- Percent-No. Compound ration age 13f Untreated Stan (lnocuiatcd) O (u) UntreatedCl (Uninoculated) I00 CH C 40 l C H N 500 92.5

\ CH,C

B r CH .C Table 23 2 CHI N 500 887 CH,--C

Concent- Percent- O No. Compound ration age of (p.p.m.) stand Referencecompound ll CH 0 (H -C ll Cl 3 CH. N-Q 500 .0 CHC CH.,C 1 N 500 100 IiHC 0 Cl CH, 0 Reference compound C H;, O 4 0 CI 500 9004 n CH-C 2 I N500 97.3

c Cl CHC N Br C H; O

C H O U ntreated II C l (lnueuluted) CHC Untreated 3 N 500 98.4(Uninoculuted) I00 /CHC Cl Fungieitle used as soil disinfectant,

Table 23-Continued Table 24-Continued Concent- Percentf Percent No.Compound ration age of No. Compound ratlon age of stand (p.p.m.) standReference compound Br 0 CH3 C H CH C CHC 3 ,N 500 91.2 4 J: N 0 500 0 CHc U H-C u Br 0 0 Reference compound Reference compound 6 (3| CH C Cl Cl4 l N 500 5.6

CH C 5 c 2 500 88.6 c

C I O C Cl Reference compound Untreated C Inoculated 0 CH C Untreated 5N 500 0.8 (Uninoculatcd) I00 CH C ll 0 Reference compound Table 24 25 Cl0 ll Concent- Percent- No. Compound ration age of 6 500 0 (p.p.m.) standCH Cl 0 ll cl CH C l l 500 Reference compound CH ,C c

H Cl 0 v Cl 7 Cl NC) 500 96.6 Cl 0 H Cl cl 2 CH C N 500 74.3 2 UntreatedB r (Uninoculated) l ()0 0 Table 25 Concent- Percent- No. Compoundration age of (p.p.m.) stand 0 Cl ll CCHSOCH ,CH 1 N l 500 92.4

C-CH Cl O 0 CI ll C---CHSOCH (CH CH; 2 N 500 87.3

C-CH Cl O 0 CI C--CHSOCH 0 3 N I 500 &

q CCH ll 0 Reference compound Cl CI 4 Cl j- N0 500 94.3

CI Cl Untreated (Inoculated) Untreated (Uninoculataed) 100 TEST 5 Eachof the test compounds in the form of wettable powders was diluted withwater to a given concentration and applied to pumpkin seedlings, whichhad been cultured in pots of 12 cm. in diameter and grown up to the 3-4leaves stage. in a proportion of 7 ml. of the dilution per pot. Afterone day. the seedlings were inoculated by spraying with a sporesuspension of Spluzeru- Ihecu fizlginm. l Days thereafter, theinfections state of the upper 4 leaves of the seedlings was observed,and the degree of damage was calculated from the infectious areaaccording to the following equation.

Infection index Degree of 2 Number of leaves damage X 100 Total numberof leaves X 5 wherein the infectious index was determined on the basisof the following criteria:

Infection index Infection area None Small Medium Large moi-c Table 26Concent- Degree No. Compound ration of (p.p.m.) damage CH 0 c (3 cl 1 HC I N 1000 9.1

C/ Cl CH O H CH 2 CH N@ 1000 41.7

Untreated 52.9

Table 27 Concent- Degree No. Compound ration of (p.p.m.) damage 0 l c. 1(II: N 500 2.3

(7 ll Cl 0 Br c 2 N 500 6.7

H Br

Table 27-Continued Coneent- Degree No Compound ration of 5 p.p.m. Jdamage Cl C 3 @i N s00 l4.6

c 10 Cl Reference compound i C Untreated 42.3

Table 28 Concent- Degree No. Compound ration of (p.p.m.) damage cu o 30\CH g 01 cu c ll c1 CH 0 g 5 Raferenca compound ca c 2 I N 1,000 48.2

CH C n 40 ca 0 Untreated 55-5 Table 29 C0ncent- Degree No. Compoundration of (p.p.mr) damage l/32 r Cl 1 N [.000 048 cH. c/ cl 2 f N L0002.3

ii Cl Cl 0 Reference compound ll H C CH:fi

Untreated 43.3

Table 30 Concent- Degree No. Compound ration of (p.p.m.) damage Cl c cHso cH 1 DN Q 000 0.3

c cl-| ll 0 Untreated 58.4

TE T 6 acid imide on various phytopathogenic fungi were in- Anti-fungalspectrumvestigated to obtain the results as set forth in the table Bymeans of the agar dilution method, the growthbelow inhibiting effects ofthe N-(3,5-dihalophenyl)imide Table 33 compounds (I) on variousphytopathogenic fungi were investigated. As typical test results, thereare shown in I Minimum Concentration the table below those of N-(3,5-Tcstfung' .l'l'lv dichlorophenyl )cyclopropanedicarboxlmide. p pCochliobolus miyabeanus 200 Table 3 l Pellicularia filamentosa 200Botrytis cinerea 4U Sclerotinia selerotiorum 40 Minimum eoncentra- Testfungi tion of inhibition Altemmia klklichhma 200 (p'p Alternaria mah 200Pyricularia oryzae 200 Pellicularia filamentosa 40 TEST 9 Botrytiscinerca 8 sclcwtiniu sclcrmimum 40 Effects of controllmg AspergzllusInger ATCC 9642: gn -a ia l g :8 By means of a method similar to that asin Test 8, the Glo ri fl ie ll a eii'i gulate 20o growth-inhibitingeffects of N-(3,5dichlorophenyl TEST 7 By means of a method similar tothat as in Test 6, the growth-inhibiting effects of N( 3 ,5dichlorophenyl)cyclopropanedicarboximide on Aspergillus m'ger ATCC 9642,which propagates on industrial products, were investigated to obtain theresults set forth in the table below.

TEST 8 Anti-fungal spectrum:

By means of the agar dilution method, the growthinhibiting effects ofN-(3,5-dichlorophenyl)glutarie glutarimide on Aspergillus niger ATCC9642 were investigated to obtain the results as set forth in the tablebelow.

Table 34 Minimum concentration Compound of inhibitiotn 40 (p.p.m.)

,Cl 2 CH N 5,000

\CH. ,-C

Br CH CH C 1! 5.000 \cH c/ Q Br Reference compound ll CH-,C C 2 ND 5.000

\cH.,-c/

Notel -5U00 means no activity at 5000 p,p.m,

TEST l0 Table 35 Minimum concentration Test fungi of inhibition (p.p.m.)

Pyricularia oryzae 200 Pellicularia filamentosa 200 Corticium rolfsii20K) Botrytis cincrea 200 Sclerotinia sclerotiorum 2()() Glomerellacingulata 200 TEST 1 1 Effects of controlling Aspergillus niger ATCC9642:

By means of a method similar to that as in Test 10, thegrowth-inhibiting effects of N-( 3 ,5dichlorophenyl)-a-chlorosuccinimide on Aspergillus niger, whichpropagates on industrial products, were investigated to obtain theresult as set forth in the following table:

Table 36 Minimum concentration Test compound of inhibition (p.p.m.)

\ ii Cl I :NQ 1000 CH TEST l2 Anti-fungal spectrum:

By means of the agar dilution method, the growthinhibitingeffects ofN-(3,5-dichlorophenyl)-ethylsulfinylsuccinimide (compound 1) and N-(3,5-dichlorophenyl)-n-butylsulfinylsuccinimide (compound 2) on variousphytopathogenic bacteria and fungi were investigated to obtain theresults as set forth in the following table:

Effects of controlling Aspergillus niger ATCC 9642:

By means of a method similar to that as in Test 12, thegrowth-inhibiting effects of dichlorophenyl)-ethylsulfinylsuccinimideand N-(3,5- dichlorophenyl)-n-butylsulfinylsucciniimide on Aspergillusnigw' ATCC 9642 were investigated to obtain the results as set forth inthe following table:

Table 38 Minimum concentration Compound of inhibition (p.p.ml)

O cl CCHSOCH CH 700 0 0 cl CHSOCH (CHQ CH; l5 Dbl j 2 x 200 c-- H Cl OAs clearly understood from the above description, theN-(3,5-dihalophenyl)imide compounds (I) are useful as anti'microbialagents, particularly as agricultural and industrial and sometimes,pharmaceutical field. In other words, they may be used as agriculturalchemicals for prevention or inhibition of plant diseases caused byphytopathogenic fungi and bacteria. They may be used also as industrialchemicals for preventing or inhibiting industrial products fromstaining.

For the above purpose, the N-(3,5-dihalophenyl)- imide compounds (I) maybe used as they are but, in most practical cases, they are extended witha suitable carrier(s) to bring them into the forms of conventionalfungicides such as dusts, wettable powders, oil sprays, aerosols,tablets, emulsifiable concentrates, pellets, granules, ointment, orpowder. These anti-microbial compositions may contain, in addition tothe N-(3,5 dihalophenyl)imide compounds (I) one or more of knownfungicides, insecticides and herbicides such as, for example,Blasticidin S, Kasugamycin, Polyoxyn, Cellocidin, Chloramphenicol,0,0-diethyl-S- benzylphosphorothiolate,O-ethyl-S,S-diphenylphosphorodithiolate,O-n-butyl-S-ethyl-S-benzylphosphorodithiolate,0,0-diisopropyl-S-benzylphosphorothiolate,O-ethyl-S-benzylphenylthiophosphonate, pentachlorobenzaldoxime,pentachlorobenzyl alcohol, pentachloromandelonitrile, pentachlorophenylacetate, iron methylarsonate, ferric ammonium methylarsonate, 'yl,2,3,4,5,6-hexachlorocyclohexane, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)-ethane, 0,0-dimethyl-O-(p-nitrophenyl) phosphorothioate, S-[ 1,2- bis(ethoxycarbonyl )ethyl] 0,0-dimethyl phosphorodithioate,O-ethyl-O-p-nitrophenyl phenylphosphonothioate, a-naphthylN-methylcarbamate, 0,0-dimethyl- O( p-nitro-m-mcthylphenyl)phosphorothioate, 3,4,5,6-tetrahydrophthalimide methyl chrysanthemate,3,4-dimethylphenyl N-mcthylcarbamate, 0,0-diethyl- O(2-isopropyl-6-methyl-4-pyrimidinyl) thiophosphate,0,0-dimethyl-2,2-dichlorovinyl phosphate, l,lbis( p-chlorophenyl)-2,2,2-trichloroethanol, l ,2- dibromoethane,l,Z-dibromo-3-chloropropane, zinc ethylene-bis(dithiocarbamate),manganese ethylenebis( dithiocarbamate 2,3-dichlorol ,4- naphthoquinone,N-( trichloromethylthio )-4- cyclohexenel ,Z-dicarboximide. N-( l, l,2,2- tetrachloroethylthio )4-cyclohexenel ,2- dicarboximide,6-mcthyl-2,3-quinoxaline dithiol cyclic carbonate,tetrachloroisophthalonitrile. sodium pdimethylaminobenzenediazosulfonate, 2,4-dichloro-6- acetic anhydride are removed bydistillation under rc- (2-chloroanilino)-S-triazine,2,4-dichlorophenoxyaduced pressure, and the residue is washed with watercetic acid, 4-chloro-2-methylphenoxyacetic acid, 3,4- and dried, wherebya desired N-(3,5-dihalophenyl)sucdichloropropionanilide,2,4-dichlorophenyl-4'- cinimide is obtained in a favorable yield. Ifnecessary, nitrophenyl ether, 2-chloro-4,6-bis(ethylamino)-S- 5recrystallization from ethanol is effected to obtain the triazine,sodium N-( l-naphthyl) phthalamate, etc. The desired product in a pureform. anti-microbial compositions may also contain one or TheN-phenylsuccinamic acid employed in the presmore of materials known tobe active as nematocides, ent process is easily obtainable according toan ordiacaricides, fertilizers, soil conditioners, soil disinfecnaryprocedure from a corresponding succinic anhytants and plant growthregulators. Examples of typical dride derivative and an anilinederivative. Typical exanti-microbial compositions according to thepresent amples of the succinic anhydride and aniline are as setinvention are as follows: forth below, but it is needless to say thatthe scope of a. Dusts obtained by dispersing at least one of the thepresent invention is not limited thereby. N-(3,5-dichlorophenyl)imidecompounds (I) as active Succinic anhydrides: ingredient to aconcentration of 0.1 to 50% by weight Z-Methylthio succinic anhydride inan inert carrier, e.g. talc, diatomaceous earth, wood Z-Ethylthiosuccinic anhydride flour or clay. Z-n-Propylthio succinic anhydride b.Wettable powders obtained by dispersing at least py Succinic anhydrideone of the N-(3,5-dichlorophenyl)imide compounds Y i inic anhydride (1)as active ingredient to a concentration of 0.1 to Z-lSO-ButylthioSuccinic anhydride 95%, preferable 0.1 to 80%, by weight in an inertadz-sec-Butylthio Succinic anhydride sorbent carrier, e.g. diatomaceousearth, together with 2-tel't-Buty1thi0 Succinic anhydride a wettingand/or dispersing agent such as an alkali z'n-Amylthio Succinicanhydride metal salt ofa long aliphatic sulfate chain, a partly neu ySuccinic anhydride tralized sulfuric acid derivative of either apetroleum ztert'Amylthio succinic anhydrid oil or a natural occurringglyceride or a condensation z'Hexylthlo Succinic anhydride product of analkylene oxide with an organic acid. p y Succinic anhydride 0.Emulsifiable concentrates obtained by dispersing zoctylthiP f 'fanhydride at least one of the N-(3,5-dichlorophenyl)imide comzNonylthfoanhydride pounds (I) as active ingredient to a concentration ofzDecylthlo Succlmc anhydnde 0.1 to 50% by weight in an organic solvent,e.g. diz'phenylthlo Succml? anhydI:id e methyl sulfoxide, plus anemulsifier such as an alkali z'wchlorophenylthlf) f anhydnde metal saltof a long aliphatic sulfate chain, a partly neuz (m'chlorophenyltlllo)SUCCWC anhydlide tralized sulfuric acid derivative of either a petroleum5 z (p'chlorophenylthl.o) i i anhydride oil or a natural occurringglyceride or a condensation 2'(O'Methylpheny M119) i? anhydnqe productof an alkylene oxide with an organic acid. ii a g i i i gl sucfinllcanhydllde d. Compositions of the N-(3,5-dichlorophenyl)imide 2 F i s icompounds (I) formulated in the manner commonly 2; g g li gi an y ndeemployed in the art for the preparation of microbicidal 4O m eihyl a min o succinicyanlhjdride granule? dusts and aerosols Z-(Di-n-propylamino)succinic anhydride Practical presently-preferred embodiments of the 2(Di iSo prOpylaminO) Succinic anhydride present invention areillustrativcly shown below with 2 (Di n butylaminO) Succinic anhydridereference to examples, in which parts and percentages 2 (Di isobutylamino)succinic anhydride r y weight 2-( Di-n-amylamino) succinicanhydride Examples l59 are concerned with the syntheses of 2 (Di isoamylamino) succinic anhydride the present C p 2-Dihexylamino succinicanhydride Z-Pyrrolidino succinic anhydride EXAMPLES 1 1 3 2-P1peridinosuccinic anhydride 2-Morphollno succinic anhydride Anilines: Standardoperational process for the syntheses of the 3,5 Difl ili presentcompounds: 3,5-Dichloroaniline A mixture comprising O.l mole of N-(3,5-3,5 Dib oanili e dihalophenyl)succinamic acid, 50 ml. of acetic anhya3,5-Diiod aniline dride and l g. of anhydrous sodium acetate is fed to aSyntheses were effected according to the aboveml. four-necked flask andis heated with stirring at mentioned operational process to obtain theresults as 100C. for 1 hour. Thereafter, the acetic acid and shown inthe following table:

Table 39 Obtained-N4 3,5-dihalophenyl )-imide compound E V I PhysicalElementary analysis ample Succinamic acid Structural formula Yieldconstant (X: halogen atom) xm No. (/0 (0 W) CH,.,CH2S\ v CHCOOH c (1)CHZCONH Table 39 Obtained-N-( 3,5-dihalophenyl )-imide compound [5,(Physical Elementary analysis ample Succinamic acid Structural formulaYield constant (X: halogen atom) No. (71) 1 W?) CHHCHR CH;,CH2/N\CHCOOHcl CHCONH c1 PHQCPH m.p. Calcu- (c1) or 95 95- lated: 5.12 8.89 22.50 8cl CHIC. 96.5 53.35

c1-1 coo1-1 cl Cl 11 Found: 505 8.93 22.64 c1-1 c1-1 53.23

/NCHCONH cH.,c1-1. c

c1-1c0o1-1 Ol OI H4 1-1. macaw-Q I. G (C 1) CH., mp Cab (01) C cu- 9 D-N39- luted: 6.52 7.54 910 u coon C cl CH 9] 58-22 [CH"(CH2)2CH2]2NCHCONHQ Found: 6.67 7.42 l9.00

D" cl11c0011 0 Cl or Calcu- (Cl) CH2CONHQ lated: 4.51 8.95

c Cl I 2.6l N 97 53.69 10 CIHQCOOH q CCH 87 Found: 4.40 8.78 2 .76

EN CH-CON 51 :1 o -cucoou c1 CH CONH- W 2 QC. or cl CH N: Calcu- D Im.p. 4.93 8.56 1.67

N H. .COOH CH., 90 11s- 55.06 11 c1 I 121 Found: 5.05 8.42 21.32 O4-CHCONHQ O 55.22

h o N-CHCOOH cH coNw-g V q Cf Calcuc1 cl or I CH m.p. latcd: 4.29 8.512l.54 12 Cl N N 0 209- 51.03

cH. .cooH *fi 2 210 r l ng; 4.13 8.27 21.31

0 CL N CHCONH \Br CHCOOH 1 I Br or cn cowng a Br Calcu- (B D-N S m.pluted: 2.51 3.18 30.23 OCH: l6l Found: 247 3.30 36.44 CHZCOOH 43.20 L Br0 -CH-CONH Q EXAMPLES 14-20 Standard operational process:

A mixture comprising 0.1 mole of an N-phenylcyclopropanedicarboxylicacid monoamide derivative. 50 g.

of acetic anhydride and l g. of anhydrous sodium acetate is fed to a ml.four-necked flask and is heated with stirring at 100C. for 30 minutes.Thereafter, the acetic acid and acetic anhydride are removed by distil-

1. AN N-(3,5-DIHALOPHENYL) IMIDE COMPOUND REPRESENTED BY THE FORMULA, 2.An N-(3,5-dichlorophenyl)imide compound represented by the formula, 3.The compound of the formula,
 4. The compound of the formula,